Lubricating oil compositions containing sulfurchlorinated styrene derivatives

ABSTRACT

There is provided a lubricating oil composition which comprises a major amount of lubricating oil and a minor amount of an extreme pressure property improving additive which is a compound having the formula   WHERE R is hydrogen, alkyl of 1 to 4 carbon atoms or chlorine, R&#39;&#39;&#39;&#39; is hydrogen or chlorine, R&#39;&#39; is hydrogen or methyl and x is a number from 1 to 10, usually not over 6 and normally 1 to 3. The additive is made by reacting styrene or the appropriate substituted styrene with a sulfurizing agent such as sulfur monochloride or a dichlorosulfane, e.g., sulfur dichloride.

United States Patent 1 1 Dalter et al.

[ 51 Aug. 19, 1975 I LUBRICATING OIL COMPOSITIONS CONTAININGSULFURCl-ILORINATED STYRENE DERIVATIVES [75] Inventors: Raymond S.Dalter, Montgomery;

Sidney S. White, Westchester, both of Ohio [73] Assignee: CincinnatiMilacron Chemicals Inc.,

. Reading, Ohio [22] Filed: Jan. 10, 1974 [21] App]. No.: 432,395

Primary E.\-aminerDelbert E. Gantz Assistant Examiner-I. VaughnAttorney, Agent, 0:- Firm-Cushman, Darby & Cushman [-5 7] ABSTRACT Thereis provided a lubricating oil composition which comprises a major amountof lubricating oil and a minor amount of an extreme pressure propertyimproving additive which is a compound having the formula where R ishydrogen, alkyl of 1 to 4 carbon atoms or chlorine, R" is hydrogen orchlorine, R is hydrogen or methyl and x is a number from 1 to 10,usually not over 6 and normally 1 to 3. The additive is made by reactingstyrene or the appropriate substituted styrene with a sulfurizing agentsuch as sulfur monochloride or a dichlorosulfane, e.g., sulfurdichloride.

16 Claims, N0 Drawings LUBRICATING OIL COMPOSITIONS CONTAININGSULFURCI-ILORINATED STYRENE DERIVATIVES FIELD OF THE INVENTION Thisinvention relates to lubricating oil compositions containing sulfurchlorinated styrene and substituted styrene derivatives. In particular,the invention relates to lubricating oil compositions containing sulfurchlorinated styrene derivatives in minor amount sufficient to improveextreme pressure properties thereof, e.g., to create high load carryingcapacity and long timetofailure characteristics.

DESCRIPTION OF PRIOR ART Organic sulfur chlorinated compounds have longbeen known as additives for lubricating oils. These additives impart tothe lubricating oil desirable characteristics such as high speed shockresistance, good load carrying capacity, and anti-wear properties. Theor ganic sulfur chlorinated compounds disclosed prior to this inventionwere aliphatic sulfur chlorinated compounds prepared from an aliphaticolefin and sulfur monochloride or sulfur dichloride.

Veatch U.S. Pat. No. 2,592,264 discloses methods of introducing sulfurinto motor oil" by reaction of the motor oil with sulfur monochlorideusing a paraffin oil diluent in the presence of alkali carbonates totake up hydrogen chloride produced and to eliminate loosely boundchloride. The use of volatile solvents such as heptane is alsodisclosed.

Rausch U.S. Pat. No. 2,943,990 discloses improved cutting oils obtainedby sulfurchlorinating a mineral oil. The products are stated to have lowsludge forming tendencies.

In Eby U.S. Pat. No. 2,708,l99 there is disclosed a method of producingpolysulfides from olefins having from 6 to 30 carbon atoms andsufficient sulfur to fall in the range of from 2 to 3 sulfur atoms perdegree of unsaturation in the starting olefin. The products are preparedfrom sulfur chlorinated aliphatic olefins'and are claimed to have goodlubricating characteristics. When applied to olefins of less than 6carbon atoms the products are found to be insoluble in lubricating oils.

Myers U.S. Pat. No. 3,471,404 discloses a method of overcoming the lowoil solubility of chlorosulfurized lower olefins by first reacting a lowmolecular weight olefin with sulfur monochloride then reacting thechloro-alkyl sulfide or polysulfide with an alkali sulfide convertingthe chloro groups to mercaptans and polysulfides.

The claimed advantage of the high sulfur concentration is that thematerial is light in color and can be diluted with any of the commoncutting oils to a predetermined sulfur concentration.

Applicants have discovered that bis(B-chloro-B- phenyl ethyl) sulfideand bis(,B-chloro-B-phenyl ethyl)- polysulfide and derivatives, whencombined with lubricating oils, give compositions having exceptionallygood extreme pressure lubricating characteristics.

The compounds employed in theinvention have the formula:

-C-CH2 where R is hydrogen, alkyl of l to 4 carbon atoms or chlorine, R"is hydrogen or chlorine, R is hydrogen or methyl and is a number from 1to 10, usually not over 6, normally 1 to 3 and most preferably 1 to 2.Typical compounds which can be employed in the invention include:

bis( ,B-chloro-B-phenylethyl )sulfide,

bis( B-chloro-B-phenylethyl )disulfide,

bis( fichloro-B-phenyl ethyl )trisulfide,

bis( B-chloro-B-phenylethyl )tetrasulfide,

bis( ,B-chloro-B-phenylethyl )hexasulfide,

bis( B-chloroBmethyl-B-phenylethyl )sulfide,

bis( B-chloro-B-methyl-B-phenylethyl )disulfide, bis(B-chloro-,8-methylB-phenylethyl )trisulfide, bis(B-chloro-B-methyl-B-phenylethyl )tetrasulfide,

bis( B-chloro-B-p-tolylethyl )sulfide,

bis( B-chloro-B-p-tolylethyl )disulfide,

bis( Bchloro-B-o-tolylethyl )sulfide,

bis( B-chloro-B-m-tolylethyl )disulfide,

bis[ B-chloro-B-( p-S-butylphenyl )ethyl]sulfide, bis B-chloro-B-(p-t-butylphenyl )ethyl disulfide bis[B-chloro-B-( p-ethylphenyl)ethyl]sulfide, bis[ B-chloro-B-( p-ethylphenyl )ethyl disulfide,

bis( B-chlorofi-p-chlorophenylethyl )sulfide bis(,B-chloro-B-p-chlorophenylethyl )disulfide,

bis( B-chloro-B-o-chlorophenylethyl )sulfide, bis(,8-chloro-B-o-chlorophenylethyl )disulfide,

bis( B-chloro-B-Z,4-dichlorophenylethyl )sulfide, bis(B-chloro-B-Z,4-dichlorophenylethyl )disulfide.

DESCRIPTION OF SPECIFIC EMBODIMENTS Thebis(BehloroB-phenylethyl)sulfides or polysulfides of this invention maybe derived from styrene itself or from a substituted styrene. Thesulfides and polysulfides from styrene, a-methylstyrene and vinyltolueneare the preferred embodiments of the invention because the startingmaterials are readily available and they give products havingexceptionally good extreme pressure lubricating properties. To obtainthe oil additives of this invention styrene or a substituted styrene isreacted with sulfur monochloride or a dichlorosulfane, e.g., sulfurdichloride at to C with or without a solvent inert to both reactants.The reaction is allowed to proceed to completion over a period of 3 to 5hours. The product can then be washed with a small amount of alkali toneutrality or alternately blown with air to remove any retained hydrogenchloride. Without further treatment the product obtained can be used incombination with a lubricating oil as a high temperature lubricant andas an extreme pressure lubricant.

As substituted styrenes there can be used for example styrene, a-methylstyrene, p-vinyl toluene, o-vinyl toluene, m-vinyl toluene, p-ethylstyrene, p-t-butyl styrene, o-t-butyl styrene, m-t-butyl styrene,m-n-butyl styrene, p-n-butyl styrene, p-chlorostyrene, o-chlorostyrene,mchlorostyrene, 2,4-dichloro styrene, etc.

The bis(B-chloro-B-phenyl ethyl)sulfides and polysulfides employed inthe present invention can be prepared for example in the mannerdescribed in Hageman German Offenlegungsschrift 2,040,817, the entiredisclosure of which is incorporated by reference.

The bis(B-chloro-B-phenyl ethyl)sulf1des disulfides and higherpolysulfides are oil soluble extreme pressure additives for cuttingfluids, lubricating oils, transmission fluids, or greases. Thesesulfides, disulfides and higher polysulfides can be used in conventionallubrieating base media, such as naphthenic or paraffmic mineral oils andsynthetic lubricants, such as hydrocarbon fluids, glycol ether fluids,polysiloxane fluids, e.g., poly(dimethyl siloxane) fluids, acetals,polyphenyl ethers and the synthetic ester lubricants produced frommonohydric alcohols and polycarboxylic acids and polyhydric alcohols,such as trimethylolpropane and pentaerythritol and carboxylic acidshaving from six to twenty carbon atoms, e.g., adipic acids sebaeic acidand 1.20 eicosanediocic acid.

The extreme pressure additives of the present invention are preferablyemployed with hydrocarbon oils, most preferably paraffinic mineral oils.The lubricating compositions employed in the invention contain a majoramount of a lubricating oil and a minor amount suffieient to improveextreme pressure properties thereof of the mono or polysulfides of thetypes set forth above. Thus the composition can contain 0.001 to 20percent, more usually 0.01 to percent, preferably not over 5 percent ofthe mono or polysulfide additive. Of course, mixtures ofbis(B-chloro-phenyl ethyl) sulfides and/or polysulfldes can be used inthe invention.

EVALUATIONS OF LUBRICATING COM POSITIONS The lubricating compositions ofthis invention were evaluated by the Mean Hertz Load Test, the FalexTest, and the Shell Four-Ball Wear Test. The Hertz Test is used todetermine the extreme pressure (EP) properties or load-carrying capacityof lubricants. The Shell Test is used to determine the relativewear-preventing properties of lubricants on sliding metal surfacesoperating under boundary lubrication conditions. The Falex Test measuresantiwear properties of lubricants under extreme pressure.

The results of the Mean Hertz Load Test are listed in Table 1.

Table 11 lists results of the Shell Four-Ball Wear Tests showing averagescar diameter.

In comparing the capabilities of various lubricants, the results of boththe Extreme Pressure and Wear Test should be considered. Lubricants thathave good extreme pressure properties are not always equally effectivein reducing wear rates at less severe loads, and conversely.

The Wear-Load Test is conducted at a constant load, constanttemperature, set rpm, and specific duration of time. The scar diameterof the balls on the wear load is reported and used in comparison withthe scar diameters from tests of other lubricants.

Table 111 lists experimental results of the Falex Extreme Pressure Testson the base oil (100/100 naphthenic oil), bis-(B-chloro-B-phenylethyl)disulfide, bis(B-chloro-B-tolyl ethyl )disulfide,

TABLE I MEAN HERTZ LOAD TEST RESULTS EXTREME PER CENT BY PRESSUREADDITIVE WEIGHT VALUE bis([3-chloro-B-phenyl cthyl)- 0.25 33.37

disulfide 0.50 52.31 1.00 67.54 2.00 79.54 5.00 92.58 Sulfumhlorinatcdalpha pinene 0.50 37.52 1.00 50.50 2.00 61.43

All experiments were carried out in a mid-continent SAE oil.*Sulfurchlorinated alpha pinene with and without other sulfurchlorinated olefins or fatty esters is the most commonly used commercialoil additive for extreme pressure luhricaliort for heavy duty Cuttingoperations.

TABLE II SHELL FOUR-BALL WEAR TEST RESULTS AVERAGE PER CENT BY SCARADDITIVE WEIGHT DIAMETER bis( B-chloro-B-phenyl ethyl disulfide 0.250.593 mm 0.50 0.646 mm 1.00 0.657 mm 2.00 0.883 mm 5.00 0.699 mmSulfurchlorinated alpha pinene 0.50 0.593 mm 1.00 0.670 mm 2.00 0.732 mmTABLE III FALEX TEST RESULTS CONCEN- POUNDS TRATION PRESSURE ADDlTlVEPER CENT APPLIED Base Oil /100*** naphthenic oil) 100.00 F l.000*bis(B-chloro-fiphenyl ethyl) disulfide 0.05 P 4,500** 0.10 P 4,500 0.25P 4,500 0.50 P 4.500 1.00 P 4,500 Sulfur chlorinated alpha-pinene 0.50 F3,500 1.00 F 3,750 I 2.00 F 4,250 bis(/3-chloroB-methyLB-phenyl ethyl)disulfide 0.25 F 4,250 bis( B-chloro-B-tolyl ethyl disulfide 0.25 P4,500

'F indicates failure at the corresponding pressure. "P indicates testpassage at the pressure limit of the test method. *"Saybolt Universalseconds at 100 F,

bis(B-ehloro-B-methyl-B-phenyl ethyl)disulfide, and sulfur chlorinatedalpha-pinene. The latter with or without other added sulfur'chloride andolefins is the most widely used commercial lubricating oil additive forheavy duty cutting operations.

From these data it can be observed that bis(B-chloro- B-phenylethyl)disulfide and its derivatives give test results superior to thecommon commercial product sulfurchlorinated alpha-pinene. In addition,the products of this invention show higher flash-fire properties andhave a much lighter color than the sulfur chlorinated alpha-pinene.

For example, bis(B-chloro-B-phenyl ethyl )disulfide and its derivativeare typically ASTM Dl500-color l-3 C -CH S where R is hydrogen, alkyl ofl to 4 carbon atoms or chlorine, R" is hydrogen or chlorine, R ishydrogen or methyl and is a number from 1 to l0.

2. A lubricating oil composition according to claim 1, wherein is l to6.

3. A lubricating oil composition according to claim 2 wherein is l to 4.

4. A lubricating oil composition according to claim 3 wherein is l to 2.

5. A lubricating oil composition according to claim 4 wherein x is 2.

6. A lubricating oil composition according to claim 4 wherein thelubricating oil is a hydrocarbon oil.

7. A lubricating oil composition according to claim 6 wherein the oil isa mineral oil.

8. A lubricating oil composition according to claim 1 in which saidadditive is bis(B-chlor0-B-phenyl ethyl) sulfide.

9. A lubricating oil composition according to claim 1 in which saidadditive is bis(Bchloro-/3-phenyl ethyl )disulfide.

10. A lubricating oil composition according to claim 1 in which saidadditive is bis(B-chloro-B-methyl-B- phenyl ethyl)-sulfide.

l]. A lubricating oil composition according to claim 1 in which saidadditive is bis(B-chloro-B methyl-B- phenyl ethyl)-disulfide.

12. A lubricating oil composition according to claim 1 in which saidadditive is bis(,8-chloro-B-tolyl ethyl)- sulfide.

13. A lubricating oil composition according to claim 1 in which saidadditive is bis(B-chloro-B-tolyl ethyl )disulfide.

14. A lubricating oil composition according to claim 4 wherein theadditive is present in an amount of 0.001 to 20 percent.

15. A lubricating oil composition according to claim 14 wherein theadditive is present in an amount of 0.01 to 20 percent.

16. A lubricating oil composition according to claim 15 wherein theadditive is present in an amount of 0.05

to 5 percent.

Disclaimer 3,900,409.Raym0nd S. Daltew, Montgomery, and Sidney S. White,Westchester, Ohio. LU BRIOATIN G OIL COMPOSITIONS CON TAIN INGSULFUR-CHLORINATED STYREN E DERIVATIVES. Patent dated Aug. 19, 1975.Disclaimer filed June 28, 1976 by the assignee, Oz'ncinnatz' MilacwonOhemz'cgls, Ina. Hereby enters this disclaimer to claims 1-9 and 14-16of said patent.

[Oficz'al Gazette August 10, 1976.]

1. A LUBRICATING OIL COMPOSITION COMPRISING: A. A MAJOR AMOUNT OF ALUBRICATING OIL, AND B. A MINOR AMOUNT SUFFICIENT TO IMPROVE EXTREMEPRESSURE PROPERTIES THEREOF OF AN ADDITIVE HAVING THE FORMULA:
 2. Alubricating oil composition according to claim 1, wherein x is 1 to 6.3. A lubricating oil composition according to claim 2 wherein x is 1 to4.
 4. A lubricating oil composition according to claim 3 wherein x is 1to
 2. 5. A lubricating oil composition according to claim 4 wherein x is2.
 6. A lubricating oil composition according to claim 4 wherein thelubricating oil is a hydrocarbon oil.
 7. A lubricating oil compositionaccording to claim 6 wherein the oil is a mineral oil.
 8. A lubricatingoil composition according to claim 1 in which said additive is bis( Beta-chloro- Beta -phenyl ethyl) sulfide.
 9. A lubricating oil compositionaccording to claim 1 in which said additive is bis( Beta -chloro- Beta-phenyl ethyl)disulfide.
 10. A lubricating oil composition according toclaim 1 in which said additive is bis( Beta -chloro- Beta -methyl- Beta-phenyl ethyl)-sulfide.
 11. A lubricating oil composition according toclaim 1 in which said additive is bis( Beta -chloro- Beta -methyl- Beta-phenyl ethyl)-disulfide.
 12. A lubricating oil composition according toclaim 1 in which said additive is bis( Beta -chloro- Beta -tolylethyl)sulfide.
 13. A lubricating oil composition according to claim 1 inwhich said additive is bis( Beta -chloro- Beta -tolyl ethyl)disulfide.14. A lubricating oil composition according to claim 4 wherein theadditive is present in an amount of 0.001 to 20 percent.
 15. Alubricating oil composition according to claim 14 wherein the additiveis present in an amount of 0.01 to 20 percent.
 16. A lubricating oilcomposition according to claim 15 wherein the additive is present in anamount of 0.05 to 5 percent.